EP2096082B1 - Verfahren zur Herstellung von Trichlorsilan - Google Patents

Verfahren zur Herstellung von Trichlorsilan Download PDF

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Publication number
EP2096082B1
EP2096082B1 EP09153800.9A EP09153800A EP2096082B1 EP 2096082 B1 EP2096082 B1 EP 2096082B1 EP 09153800 A EP09153800 A EP 09153800A EP 2096082 B1 EP2096082 B1 EP 2096082B1
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Prior art keywords
tcs
hydrogen
decomposition
polymers
distillation
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French (fr)
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EP2096082A1 (de
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Noboru Tachino
Hisayuki Takesue
Harumi Satoh
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
    • C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B01J2219/00063—Temperature measurement of the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
    • B01J2219/00135—Electric resistance heaters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to a method for manufacturing trichlorosilane by decomposing compounds (hereinbelow, referred to as "polymers") containing high-boiling chlorosilane, which are generated in a polycrystalline silicon manufacturing process.
  • the present invention relates to a method for manufacturing trichlorosilane by decomposing polymers that have been separated in a chlorination step or polymers that have been separated from an exhaust gas of a polycrystalline silicon manufacturing process.
  • the high-purity polycrystalline silicon that can be used as a semiconductor material is mainly manufactured by the Siemens process in which, for example, trichlorosilane (SiHCl 3 ; abbreviated "TCS”) and hydrogen are used as raw materials, a gas mixture thereof is introduced into a reactor and brought into contact with heated silicon rods, and silicon is deposited on the surfaces of the silicon rods due to the hydrogen reduction or thermal decomposition of the trichlorosilane at a high temperature.
  • TCS trichlorosilane
  • hydrogen hydrogen
  • the high purity trichlorosilane to be introduced into the reactor for example, is manufactured by introducing metallurgical grade silicon and hydrogen chloride into a fluidized-bed chlorination furnace to react them, chlorinating the silicon to produce crude TCS (chlorination step), and purifying the crude TCS by distillation into high purity TCS.
  • the reactor exhaust gas includes, in addition to unreacted trichlorosilane, hydrogen, and hydrogen chloride, by-products such as silicon tetrachloride (STC) and chlorosilanes including, for example, tetrachlorodisilane (Si 2 H 2 Cl 4 ) and hexachlorodisilane (Si 2 Cl 6 ).
  • STC silicon tetrachloride
  • chlorosilanes including, for example, tetrachlorodisilane (Si 2 H 2 Cl 4 ) and hexachlorodisilane (Si 2 Cl 6 ).
  • STC silicon tetrachloride
  • chlorosilanes including, for example, tetrachlorodisilane (Si 2 H 2 Cl 4 ) and hexachlorodisilane (Si 2 Cl 6 ).
  • Patent Document 1 PCT International Publication WO 02/012122
  • the chlorosilanes
  • the gas produced in the chlorination reactor includes, in addition to trichlorosilane and unreacted hydrogen chloride, by-products such as silicon tetrachloride and high-boiling chlorosilanes.
  • by-products such as silicon tetrachloride and high-boiling chlorosilanes.
  • the gas that has been produced in the chlorination reactor is purified by distillation, separated polymers undergo a hydrolytic process and are then discarded.
  • the exhaust gas of the reactor is introduced into a recovery distillation column, and after the polymers have been separated, the exhaust gas is returned to the distillation step of the chlorination step and recycled.
  • the separated polymers undergo a hydrolytic process and are then discarded.
  • the hydrolytic and the waste disposal processes are costly.
  • Patent Document 2 Japanese Unexamined Patent Application, First Publication No. H01-188414 .
  • US 2004/0131528 A1 and US 2002/183537 A1 disclose methods for decomposing disilane by introducing disilane and hydrogen chloride into a furnace and heating the mixture thereof.
  • the present invention solves the above problems in the conventional polycrystalline silicon manufacture, and provides a manufacturing technology in which polymers separated from crude TCS in the chlorination step and polymers separated from the exhaust gas in the reactor are decomposed and converted to trichlorosilane.
  • the present invention relates to a method for manufacturing trichlorosilane that solves the problems described above. The method is defined in claim 1.
  • the method of the present invention is a method for manufacturing trichlorosilane by decomposing polymers enables recovering trichlorosilane by decomposing polymers that have been separated in a polycrystalline silicon manufacturing process, enables significantly reducing the load incurred due to carrying out waste disposal by hydrolytic the polymers, increases the consumption efficiency of raw materials by recycling the recovered trichlorosilane, and enables the reduction of the polycrystalline silicon manufacturing cost.
  • the manufacturing method for example, enables recovering trichlorosilane by decomposing at least one of a polymer that has been separated in a chlorination step in a polycrystalline silicon manufacturing process and a polymer that has been separated from an exhaust gas of a reactor.
  • the recovered trichlorosilane can be recycled as a raw material for manufacturing polycrystalline silicon.
  • the manufacturing apparatus is provided with a decomposition furnace that produces trichlorosilane by heating and decomposing polymers, and because trichlorosilane is manufactured by mixing the polymers and hydrogen chloride and reacting the mixture at a predetermined temperature, it is possible to manufacture trichlorosilane by using the polymers that have been separated in the chlorination step or the polymers that have been separated from the exhaust gas of the reactor.
  • the mixture is preheated while flowing through the supply pipe inside the furnace, and it is possible to react the mixture efficiently and to increase the yield of the trichlorosilane.
  • the method of the present invention is a method for manufacturing trichlorosilane, wherein high-boiling chlorosilane compounds (referred to herein as "polymers"), which have been generated in a polycrystalline silicon manufacturing process, are mixed with hydrogen chloride and introduced into a decomposition furnace, the polymers and the hydrogen chloride are reacted at a temperature of 450°C or more, or preferably, of 450°C or more and 700°C or less, and the trichlorosilane is thereby manufactured.
  • polymers high-boiling chlorosilane compounds
  • the decomposition process includes the following reactions.
  • Polymers may include other compounds such as pentachlorodisilane (Si 2 HCl 5 ) and octachlorotrisilane (Si 3 Cl 8 ). These compounds can also be decomposed by reacting with hydrogen chloride as well as the reactions (1) and (2).
  • the manufacturing method can be applied to polymers that are separated in a manufacturing process for polycrystalline silicon.
  • An example of a process for polycrystalline silicon manufacture is shown in FIG. 1 .
  • the illustrated manufacturing system includes a fluidized-bed chlorination furnace 10 that produces crude (unrefined) TCS by reacting a metallurgical grade silicon and hydrogen chloride; a first distillation column 11 that distils the produced chlorosilanes including the crude TCS produced by the chlorination reactor 10; an evaporator 12 that evaporates purified TCS along with hydrogen, STC, and TCS that are recovered from the downstream processes to prepare raw material gas; a reactor 13 that manufactures polycrystalline silicon from the raw material gas; and a condenser 14 that separates the chlorosilanes from the exhaust gas of the reactor 13.
  • the metallurgical grade silicon and the hydrogen chloride are introduced into the fluidized-bed chlorination furnace 10, and, in a fluidized state, metallurgical grade silicon and hydrogen chloride are reacted to produce crude TCS. At this time, polymers are also generated.
  • the produced chlorosilanes which includes crude TCS, by-products, and unreacted hydrogen chloride and the like, is introduced into the distillation column 11 from the fluidized-bed chlorination furnace 10, and the crude TCS is purified by distillation.
  • the purified TCS is introduced into the evaporator 12 from the distillation column 11, and at the same time, the distillation residue in the distillation column 11 is separated from the column bottom.
  • the distillation residue includes polymers generated in the above process and the like, and distillation residue including the polymers are fed to the polymer decomposition step 30 according to an embodiment of the present invention.
  • the TCS which has been introduced from the distillation column 11, and the hydrogen, STC, and TCS, which have been recovered from the downstream steps, are introduced into the evaporator 12, and a raw material gas in which these are mixed is prepared.
  • This raw material gas is introduced into the reactor 13. Inside the reactor 13, plural silicon rods are stood, these silicon rods are heated to a temperature of 900°C or more and 1200°C or less, the raw material gas is brought into contact with surfaces of the heated silicon rods, and silicon is deposited thereon due to the hydrogen reduction and thermal decomposition of the TCS.
  • the exhaust gas of the reactor 13 contains, in addition to unreacted TCS, hydrogen, hydrogen chloride, and STC, high-boiling chlorosilanes such as tetrachlorodisilane and hexachlorodisilane that have been produced in the reactor 13.
  • This exhaust gas is introduced into the condenser 14, cooled to a temperature of about -50°C, and the chlorosilanes, which include the polymers, are liquefied and thereby separated from the exhaust gas.
  • the liquid that includes the chlorosilanes that have been separated by the condenser 14 is introduced into the distillation step 20.
  • the TCS and the STC included in the liquid are stepwise distilled and separated from the polymers.
  • the separated TCS and STC are returned to the evaporator 12 and recycled as a raw material gas component.
  • a portion of the distilled chlorosilanes including the separated STC can be used as a raw material for generating TCS.
  • a portion of the distilled chlorosilanes including STC that has been separated in the distillation step 20 is introduced into the TCS conversion step 51 via the evaporator 50.
  • STC silicon tetrachloride
  • hydrogen are reacted at a high temperature of 800°C or more and 1300°C or less to produce TCS (trichlorosilane).
  • a gas including the produced TCS is introduced into a condenser 52, and cooled to a temperature of about -50°C in the condenser 52.
  • the TCS and STC and the like are liquefied and thereby separated from the gas.
  • the separated liquid is returned to the distillation step 20.
  • the TCS and STC that have been recovered in the distillation step 20 by distillation are returned to the evaporator 12 and recycled.
  • the gas that has been extracted from the condenser 52 is introduced into the absorption-adsorption step 53, and the hydrogen that is included in the gas is recovered.
  • the recovered hydrogen is returned to the TCS conversion step 51 and recycled.
  • polymers that are included in the exhaust gas of the reactor 13 and the polymers that have been generated in the TCS conversion process are included in the distillation residue that is separated in the distillation step 20, and these polymers (distillation residue) can be introduced into the polymer decomposition step 30 according to the embodiment of the present invention and decomposed.
  • the high-boiling chlorosilanes are generally included at about 20 to 50 mass% in the distillation residue that is separated by the distillation column 11 in the chlorination step and the distillation residue that is separated in the distillation step 20.
  • the distillation residue that is separated in the distillation step 20 includes, for example, about 1 to 3 mass% TCS, about 50 to 70 mass% STC, about 12 to 20 mass% Si 2 H 2 Cl 4 , about 13 to 22 mass% Si 2 Cl 6 , and about 3 to 6 mass% other high-boiling chlorosilanes.
  • these polymers are decomposed and converted to trichlorosilane (TCS).
  • the polymer decomposition step 30 for polymers is shown in FIG 2 and FIG. 3 .
  • a cylinder 31 that retains the polymers a hydrogen chloride tank 32, a decomposition furnace 33, and a condenser 34 are provided.
  • the polymers (distillation residue) that are separated from the crude TCS in the chlorination step shown in FIG. 1 and the polymers (distillation residue) that have been separated from the exhaust gas of the reactor 13 are accumulated in the cylinder 31.
  • the hydrogen chloride gas is retained in the tank 32.
  • the gas including the TCS produced in the decomposition step 33 is fed to the condenser 34 through the discharge pipe 39, cooled to a temperature of about 30°C to about 8°C, and a condensate that includes TCS is recovered.
  • the recovered condensate is introduced into the distillation column 11 that purifies the crude TCS-containing gas of the chlorination step, the recovered TCS is purified with the crude TCS that was produced by the chlorination reactor 10, and this purified TCS can then be recycled.
  • the STC that has been produced by the decomposition furnace 33 is recovered via the condenser 34, introduced into the polycrystalline silicon manufacturing step, and can thereby be recycled.
  • the gas including the TCS produced in the decomposition furnace 33 is introduced into the chlorination reactor 10 for the polycrystalline silicon manufacturing step via the discharge pipe 39 shown in FIG. 4 .
  • the metallurgical grade silicon and the hydrogen chloride are reacted in the chlorination reactor 10, and the gas including the TCS is recycled as a portion of the raw material for generating the crude TCS.
  • the polymer containing liquid is mixed with the hydrogen chloride gas and introduced into the decomposition furnace 33.
  • the ratio of the weight of hydrogen chloride with respect to the weight of the polymer is preferably 10 to 30 mass%.
  • the amount of hydrogen chloride exceeds this ratio, the unreacted hydrogen chloride increases, and this is not preferable.
  • the amount of the polymers exceeds this ratio, powdered silicon is generated in large amounts, the facility maintenance load increases, and the operating efficiency is reduced.
  • the polymers are reacted with hydrogen chloride at a high temperature of 450°C or more and thereby converted to trichlorosilane (TCS).
  • the reaction temperature in the reactor is 450°C or more, and preferably 450°C or more and 700°C or less.
  • the temperature in the furnace is lower than 450°C, the decomposition of the polymers does not progress sufficiently.
  • the temperature in the furnace rises above 700°C, a reaction occurs in which the produced trichlorosilane reacts with the hydrogen chloride to produce silicon tetrachloride (STC), and this is not preferable because the recovery efficiency of the TCS will be decreased.
  • FIG. 4 to FIG. 6 A schematic longitudinal cross-sectional view of the decomposition furnace 33 is shown in FIG. 4 to FIG. 6 .
  • the decomposition furnace 33 has a cylindrical furnace body 41 and a cylindrical heater 35 surrounding the outer periphery of the cylindrical furnace body 41, and the entire decomposition furnace 33 is accommodated inside a cylindrical vessel 36 that is formed by an insulating material.
  • the furnace body 41 is sealed by a lid 37, and a supply pipe 38 (supply device) that supplies a mixed liquid containing polymers and hydrogen chloride into the furnace and a discharge pipe 39 (gas exhaust device) that discharges the produced gas to the outside of the furnace are provided.
  • a thermometer 40 is installed in the furnace body 41.
  • the supply pipe 38 passing through the lid 37 is provided so as to extend to the inside of the furnace body 41.
  • the supply pipe 38 has a spiral shape, and the distal end opening thereof is positioned near the bottom of the decomposition furnace 33.
  • the portion of the supply pipe 38 that extends into the furnace is not limited to a spiral shape, but may also have, for example, a meandering (serpentine) shape.
  • the TCS generating reaction progresses and the recovery rate for the TCS can thereby be increased. Note that if the mixture containing polymers and hydrogen chloride is preheated before being supplied to the decomposition furnace, there is a possibility that the polymers will remain inside the preheated portion of the pipe.
  • the supply pipe 38 is provided with a spiral shape so as to surround the outer periphery of the furnace body 41, and the lower end of the supply pipe 38 opens at the bottom portion of the furnace. According to this structure, there is an advantage in that because the spiral portion of the supply pipe 38 is close to the heater 35, the pre-heating effect is significant.
  • the decomposition furnace 33 shown in FIG. 6 has a structure in which the polymer containing liquid and the hydrogen chloride are supplied into the decomposition furnace by passing through separate supply pipes.
  • the polymer containing liquid is supplied into the furnace through the supply pipe 38A
  • the hydrogen chloride is supplied into the furnace through the supply pipe 38B.
  • the polymer containing liquid and the hydrogen chloride are mixed inside the furnace.
  • the expression stating that the polymers and the hydrogen chloride are mixed and then introduced into the decomposition furnace, as shown in FIG. 6 also includes the case in which they are supplied into the furnace through separate supply pipes are mixed inside the furnace.
  • the supply pipe 38A through which the polymer containing liquid flows, extends into the furnace by meandering in a spiral shape as shown in the figure, the polymer containing liquid is preheated while flowing through the supply pipe 38A into the furnace, the hydrogen chloride is preheated while flowing through the supply pipe 38B inside the furnace, and thus the reaction efficiency can thereby be increased.
  • the polymers and the hydrogen chloride are not mixed during the pre-heat, they do not react with each other during pre-heat, and thus there is no concern that shortcomings such as the reactants adhering to and obstructing the inside of the pipes will occur.
  • the polymers that have been separated in the chlorination step and the distillation step for the exhaust gas in the reactor are introduced into the polymer decomposition step shown in FIG. 2 .
  • the polymers are mixed with hydrogen chloride gas and introduced into the decomposition furnace shown in FIG. 3 , and they are heated to a temperature of 450°C or more and 700°C or less and reacted to produce TCS.
  • TABLE 1 and TABLE 2 show the composition of the polymers before being mixed with the hydrogen chloride, the composition (%) of the decomposed gas that is extracted from the decomposing furnace, the decomposition temperature, and the amount of the polymers and the hydrogen chloride.
  • the numerical values for the mass% in the tables are values that have been calculated based on the area%.
  • after decomposition denotes the composition of the gas that has been extracted from the decomposition furnace.
  • the Comparative Example 1 is an example in which the decomposition temperature (300°C) is lower than the range of the present invention
  • Example 9 is an example in which the decomposition temperature (900°C) is higher than the preferred range of the present invention
  • Example 10 is an example in which the supply rate (6 g/min) of the hydrogen chloride is lower than the preferred range of the present invention.
  • the polymers are decomposed to produce TCS in a manner similar to Examples 1 to 3. These results are shown in TABLE 3.
  • EXAMPLE 9 EXAMPLE 10 AFTER DECOMPOSITION AFTER DECOMPOSITION AFTER DECOMPOSITION MASS% MASS% MASS% SiH 2 Cl 2 0.1 0.1 0.1 0.2 SiHCl 3 1.0 2.0 12.9 17.9 SiCl 4 58.8 60.9 85.0 75.5 Si 2 H 2 Cl 4 15.6 14.1 0.3 0.4 Si 2 Cl 6 20.6 19.5 0.2 1.0 OTHERS 3.9 3.4 1.5 5.0 POLYMER INPUT AMOUNT - 200g/min 200g/min 200g/min HCl GAS INPUT AMOUNT - 40g/min 40g/min 6g/min DECOMPOSITION FURNACE TEMPERATURE - 300°C 900°C 520°C PRECIPITATION - SMALL AMOUNT SMALL AMOUNT LARGE AMOUNT (OPERATION SUSPENDED) (Note) The expression "before decomposition" denotes the composition of the polymer containing liquid
  • after decomposition denotes the composition of the gas that has been extracted from the decomposition furnace.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Claims (2)

  1. Verfahren zur Herstellung von Trichlorsilan (TCS), umfassend:
    a) Einbringen von metallurgischem Silicium und Chlorwasserstoff in einen Wirbelschichtofen zur Chlorierung (10), und Umsetzen, in einem fluidisierten Zustand, des metallurgischen Siliciums und des Chlorwasserstoffs, um rohes TCS und Polymere zu erzeugen;
    b) Einbringen des rohen TCS, der Polymere und von nicht umgesetztem Chlorwasserstoff aus dem Wirbelschichtofen zur Chlorierung (10) in eine Destillationskolonne (11), und Reinigen des rohen TCS durch Destillation;
    c) Einbringen des gereinigten TCS aus der Destillationskolonne (11) in einen Verdampfer (12);
    d) Einbringen von Wasserstoff, Siliciumtetrachlorid (STC) und TCS, die von den nachgeschalteten Stufen zurückgewonnen wurden, in einen Verdampfer (12), und Herstellen eines Rohstoffgases;
    e) Abtrennen des Destillationsrückstands in der Destillationskolonne (11) von dem Kolonnenboden;
    f) Zuführen des Destillationsrückstands, der in dem vorstehenden Prozess gebildete Polymere enthält, zu einer Polymerzersetzungsstufe (30);
    g) Einleiten des Rohstoffgases in einen Reaktor (13), in den mehrere Siliciumstäbe gestellt und auf eine Temperatur von 900 °C oder mehr und 1200 °C oder weniger erwärmt sind, Inkontaktbringen des Rohstoffgases mit Oberflächen der erwärmten Siliciumstäbe, und Abscheiden von Silicium darauf aufgrund der Reduktion mit Wasserstoff und der thermischen Zersetzung des TCS;
    h) Einleiten eines Abgases des Reaktors (13), das nicht umgesetztes TCS, Wasserstoff, Chlorwasserstoff, STC und hochsiedende Chlorsilane, die in dem Reaktor (13) gebildet wurden, enthält, in einen Kühler (14);
    i) Verflüssigen der Chlorsilane, die die Polymere enthalten, durch Abkühlen auf eine Temperatur von -50 °C, dadurch Abtrennen der Chlorsilane aus dem Abgas;
    j) Einbringen der Flüssigkeit, die die Chlorsilane enthält, die mit dem Kühler (14) abgetrennt wurden, in die Destillationsstufe (20);
    k) Einleiten von Wasserstoff und Chlorwasserstoff, die aus dem Kühler (14) abgezogen wurden, in eine Absorption-Adsorption-Stufe (15), Abtrennen des Wasserstoffs, und Zurückführen des abgetrennten Wasserstoffs zu dem Verdampfer (12) zum Wiederverwenden als Rohstoffgaskomponente;
    l) stufenweises Destillieren und Abtrennen des in der Flüssigkeit enthaltenen TCS und STC von den Polymeren, in der Destillationsstufe (20);
    m) Zurückführen des abgetrennten TCS und STC zu dem Verdampfer (12) und Wiederverwenden als Rohstoffgaskomponente;
    n) Einbringen eines Teils der destillierten Chlorsilane, umfassend STC, das in der Destillationsstufe (20) abgetrennt wurde, über einen Verdampfer (50) in die Stufe der Umwandlung zu TCS (51);
    o) Umsetzen, in der Stufe der Umwandlung zu TCS (51), von STC und Wasserstoff bei einer Temperatur von 800 °C oder mehr und 1300 °C oder weniger, um TCS zu erzeugen;
    p) Einleiten eines Gases, das das erzeugte TCS enthält, in einen Kühler (52), und Abkühlen auf eine Temperatur von -50 °C in dem Kühler (52), um das TCS und STC zu verflüssigen und dadurch aus dem Gas abzutrennen;
    q) Zurückführen der abgetrennten Flüssigkeit zu der Destillationsstufe (20);
    r) Zurückführen des TCS und STC, die in der Destillationsstufe (20) durch Destillation zurückgewonnen wurden, zu dem Verdampfer (12) und Wiederverwenden;
    s) Einleiten des Gases, das aus dem Kühler (52) abgezogen wurde, in eine Absorption-Adsorption-Stufe (53), und Zurückgewinnen des Wasserstoffs, der in dem Gas enthalten ist; und
    t) Zurückführen des zurückgewonnenen Wasserstoffs zu der Stufe der Umwandlung zu TCS (51) und Wiederverwenden,
    u) wobei in der Polymerzersetzungsstufe (30) der Destillationsrückstand mit dem Chlorwasserstoffgas gemischt und in den Zersetzungsofen (33) eingebracht wird,
    v) die Polymere mit dem Chlorwasserstoff bei einer hohen Temperatur von 450 °C oder mehr und 700 °C oder weniger in dem Zersetzungsofen (33) umgesetzt und dadurch zu TCS umgewandelt werden.
  2. Verfahren zur Herstellung von Trichlorsilan nach Anspruch 1, wobei eine in Schritt u) verwendete Chlorwasserstoffmenge 10 bis 30 Masse-% in Bezug auf das Polymer beträgt.
EP09153800.9A 2008-02-29 2009-02-26 Verfahren zur Herstellung von Trichlorsilan Active EP2096082B1 (de)

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EP2354090A3 (de) 2012-08-08
JP5621957B2 (ja) 2014-11-12
EP2354090A2 (de) 2011-08-10
EP2096082A1 (de) 2009-09-02
KR101573933B1 (ko) 2015-12-02
US20090220403A1 (en) 2009-09-03
CN101519205A (zh) 2009-09-02
CN101519205B (zh) 2013-09-25
KR20090093842A (ko) 2009-09-02
EP2354090B1 (de) 2018-03-28
US9533279B2 (en) 2017-01-03

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